US5008277A - N-[(alpha-perhaloalkylbenzyloxy)pyridyl]N'-benzoylurea insecticides - Google Patents

N-[(alpha-perhaloalkylbenzyloxy)pyridyl]N'-benzoylurea insecticides Download PDF

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US5008277A
US5008277A US07/374,902 US37490289A US5008277A US 5008277 A US5008277 A US 5008277A US 37490289 A US37490289 A US 37490289A US 5008277 A US5008277 A US 5008277A
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Ernest L. Plummer
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/72—Nitrogen atoms
    • C07D213/75—Amino or imino radicals, acylated by carboxylic or carbonic acids, or by sulfur or nitrogen analogues thereof, e.g. carbamates
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/36—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< directly attached to at least one heterocyclic ring; Thio analogues thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings

Definitions

  • This invention pertains to the field of benzoylurea insecticides; more specifically, it pertains to novel N-[(alpha-perhaloalkylbenzyloxy)pyridyl]-N'-benzoylurea insecticides, processes and intermediates thereto, insecticidal compositions containing such benzoylurea compounds, and to the use of such compounds for controlling insects.
  • N-[substituted pyridinyl]-N'-benzoylurea compounds are known as insecticides.
  • U.S. Pat. No. 4,173,639 and U.S. Pat. No. 4,264,605 describe such N'-benzoylurea compounds carrying a N-pyridyl substituent in which the pyridine ring also contains a hydrocarbyloxy group. It is reported that compounds of this type affect insects by interfering with their metamorphosis; that is, they disrupt the normal growth and development pattern.
  • adding an alpha-perhaloalkyl substituent to the benzyl group provides insecticides with enhanced activity, controlling certain insects at application rates as low as 1 ppm. Accordingly, the N-[(alpha-perhaloalkylbenzyloxy)pyridyl]-N'-benzoylurea compounds of this invention are described by the formula ##STR2## in which
  • R A is selected from the group consisting of -hydrogen, -halogen, -lower alkyl, -lower alkoxy, -benzyl, and -benzyloxy;
  • R B is selected from -hydrogen and -halogen
  • R C and R D are both -hydrogen or together constitute a -COCO- bridge
  • R is a perhaloalkyl substituent
  • R 3 is selected from the group consisting of -hydrogen, -halogen and -phenylthio
  • R 4 is selected from the group consisting of -hydrogen, -halogen, -lower alkyl, -lower alkoxy, -lower alkoxyalkyl, -lower haloalkoxy, -lower alkylthio, -lower, alkylsulfonyl, and -dialllylamino; or
  • R 3 and R 4 at adjacent ring positions constitute a --OCH 2 O--, --CH 2 C(CH 3 ) 2 O--, or --CF 2 CF 2 O-- bridge;
  • R 5 is -hydrogen or -lower alkyl.
  • halo and halogen when employed herein mean fluorine, chlorine or bromine.
  • lower modifying "alkyl, " “alkoxy,” and the like implies a straight or branched hydrocarbon chain of 1-6, preferably 1-3, carbon atoms;
  • halo coupled with another term means one or more hydrogen atoms has been replaced by halogen;
  • perhalo coupled with another term means all the hydrogen atoms have been replaced by halogen.
  • R A and R B are in the 2-and 6-positions, respectively.
  • N-(3-pyridinyl) compounds are preferred, with R 5 at the 5-position.
  • the preferred compounds have the R 3 and R 4 substituents in the 3- and 4-positions, respectively.
  • insecticidal compositions comprising an insecticidally effective amount of at least one of the aforesaid benzoylurea compounds in admixture with an agriculturally acceptable carrier.
  • this invention includes a method of controlling insects which comprises applying to plants upon which the insects feed and where control is desired an insecticidally effective amount of at least one of the aforesaid N-[(alpha-perhaloalkylbenzyloxy)pyridyl]-N'-benzoylurea compounds.
  • 5-Amino-3-methyl-2-[1-(2,3-dihydro-2,2-dimethylbenzofuran-5-yl)-2,2,3,3,3-pentafluoropropoxy]pyridine was prepared from 2,2,3,3,3-pentafluoro-1-(2,3-dihydro-2,2-dimethylbenzofuran-5-yl)propan-1-one, by the method of Example 42.
  • 2-Chloro-3-methyl-5nitropyridine was used in place of 2-chloro-5-nitropyridine.
  • the mixture was extracted with three 150 ml portions of diethyl ether.
  • the extracts were combined and washed in succession with 200 ml of a 2N hydrochloric acid solution, 200 ml of a saturated aqueous sodium chloride solution, and 200 ml of a 2N aqueous sodium hydroxide solution.
  • the washed extract was dried over anhydrous magnesium sulfate and filtered.
  • the solvent was evaporated under reduced pressure, leaving an oil.
  • the reaction described above was repeated six additional times.
  • the residual oils from the seven experiments were combined and subjected to column chromatography on silica gel, eluting with toluene, yielding a yellow oil.
  • the benzoylureas In the normal use of the insecticidal benzoylureas of the present invention, the benzoylureas usually will not be employed free from admixture or dilution, but ordinarily will be used in a suitable formulated composition compatible with the method of application and comprising an insecticidally effective amount of benzoylurea.
  • the benzoylureas of this invention like most pesticidal agents, may be blended with the agriculturally acceptable surface-active agents and carriers normally employed for facilitating the dispersion of active ingredients, recognizing the accepted fact that the formulation and mode of application of an insecticide may affect the activity of the material.
  • the present benzoylureas may be applied, for example, as sprays, dusts, or granules to the area where pest control is desired, the type of application varying of course with the pest and the environment.
  • the benzoylureas of this invention may be formulated as granules of large particle size, as powdery dusts, as wettable powders, as emulsifiable concentrates, as solutions, and the like.
  • Granules may comprise porous or nonporous particles, such as attapulgite clay or sand, for example, which serve as carriers for the benzoylureas.
  • the granule particles are relatively large, a diameter of about 400-2500 microns typically.
  • the particles are either impregnated with the benzoylurea from solution or coated with the benzoylurea, adhesive sometimes being employed.
  • Granules generally contain 0.05-10%, preferably 0.5-5%, active ingredient as the insecticidally effective amount.
  • Dusts are admixtures of the benzoylureas with finely divided solids such as talc, attapulgite clay, kieselguhr, pyrophyllite, chalk, diatomaceous earths, calcium phosphates, calcium and magnesium carbonates, sulfur, flours, and other organic and inorganic solids which act as carriers for the insecticide. These finely divided solids have an average particle size of less than about 50 microns.
  • a typical dust formulation useful for controlling insects contains 1 part of benzoylurea, such as N-[[[[[2-(2,2,2-trifluoro-1-phenylethoxy)-3-methyl]pyridin-5-yl]amino]carbonyl]-2-chlorobenzamide, and 99 parts of talc.
  • the benzoylureas of the present invention may be made into liquid concentrates by dissolution or emulsification in suitable liquids and into solid concentrates by admixture with talc, clays, and other known solid carriers used in the pesticide art.
  • the concentrates are compositions containing, as an insecticidally effective amount, about 5-50% benzoylurea, such as N-[[[[2-(2,2,2-trifluoro-1-phenylethoxy)-3-methyl]pyridin-5-yl]amino]carbonyl]-2-chlorobenzamide, and 95-50% inert material, which includes surfaceactive dispersing, emulsifying, and wetting agents, but even higher concentrations of active ingredient may be employed experimentally.
  • the concentrates are diluted with water or other liquids for practical application as sprays, or with additional solid carrier for use as dusts.
  • Typical carriers for solid concentrates include fuller's earth, clays, silicas, and other highly absorbent, readily wetted inorganic diluents.
  • a solid concentrate formulation useful for controlling insects contains 1.5 parts each of sodium lignosulfonate and sodium laurylsulfate as wetting agents, 25 parts of N-[[[[2-(2,2,2-trifluoro-1-phenylethoxy)-3-methyl]pyridin-5-yl]amino]carbonyl]-2-chlorobenzamide, and 72 parts of attapulgite clay.
  • Manufacturing concentrates are useful for shipping low melting products of this invention. Such concentrates are prepared by melting the low melting solid products together with one percent or more of a solvent to produce a concentrate which does not solidify on cooling to the freezing point of the pure product or below.
  • Useful liquid concentrates include the emulsifiable concentrates, which are homogeneous liquid or paste compositions readily dispersed in water or other liquid carriers. They may consist entirely of the benzoylurea with a liquid or solid emulsifying agent, or they may also contain a liquid carrier such as xylene, heavy aromatic naphthas, isophorone and other relatively nonvolatile organic solvents. For application, these concentrates are dispersed in water or other liquid carriers and normally applied as sprays to areas to be treated.
  • Typical surface-active wetting, dispersing, and emulsifying agents used in pesticidal formulations include, for example, the alkyl and alkylaryl sulfonates and sulfates and their sodium slats; alkylamide sulfonates, including fatty methyl taurides; alkylaryl polyether alcohols, sulfated higher alcohols, polyvinyl alcohols; polyethylene oxides; sulfonated animal and vegetable oils; sulfonated petroleum oils; fatty acid esters of polyhydric alcohols and the ethylene oxide addition products of such esters; and the addition products of long-chain mercaptans and ethylene oxide.
  • the surface-active agent when used, normally comprises about 1-15% by weight of the insecticidal composition.
  • compositions include simple solutions of the active ingredient in a solvent in which it is completely soluble at the desired concentration, such as acetone or other organic solvents.
  • An insecticidally effective amount of benzoylurea in an insecticidal composition diluted for application is normally in the range of about 0.001% to about 8% by weight.
  • spraying and dusting compositions known in the art may be used by substituting the benzoylureas of this invention into compositions known or apparent in the art.
  • insecticidal compositions of this invention may be formulated with other active ingredients, including other insecticides, nematicides, acaricides, fungicides, plant growth regulators, fertilizers, etc.
  • active ingredients including other insecticides, nematicides, acaricides, fungicides, plant growth regulators, fertilizers, etc.
  • an insecticidally effective amount of benzoylurea be applied to plants upon which insects feed and whose control is desired.
  • an insecticidally effective amount will be about 0.1-2.0 kg/ha.
  • the benzoylureas of this invention were tested by incorporating the compounds into the diet of second instar southern armyworm (Spodoptera eridania) and cabbage looper (Trichoplusia ni). The tests were conducted at rates of 200, 20, and 2 ppm, using ten larvae per replicate and two replicates per rate. Each test was read one day, three to five days, and six to eleven days after infestation to determine the number dead after at least one molt.
  • test media consisted of a clay formulation (dust) of the test compound mixed with the insect diet.
  • the components of the test media were:
  • the agar was dissolved with heating in one-half the water and was brought to a boil. Simultaneously, all other ingredients except the formalin were placed in a blender with the remaining water and were reduced to a smooth, homogenous mixture. This mixture was added to the boiling agar. Immediately, the formalin was added with mixing.
  • the compounds of this invention were formulated as a dust on a clay base.
  • the dust consisted of the following:
  • formulations were prepared by mixing the active ingredient (i.e. the test compound) with the dry base.
  • Test media containing 200 ppm of the test compound were prepared by making a ⁇ stock solution ⁇ from 1000 mg of a 5% dust formulation stirred well with 5 ml of distilled water in a vial. One milliliter of the ⁇ stock solution ⁇ was added to 50 ml of warm, i.e. molten, insect diet in a plastic petri dish which was then mixed thoroughly. After cooling to room temperature, the gelled test media were infested with test larvae and covered.

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Abstract

N-[(Alpha-perhaloalkylbenzyloxy)pyridyl]-N'-benzoylurea compounds of the following structural formula are useful insecticides: ##STR1## in which RA is selected from the group consisting of -hydrogen, -halogen, -lower alkyl, -lower alkoxy, -benzyl, and -benzyloxy;
RB is selected from -hydrogen and -halogen;
RC and RD are both -hydrogen or together constitute a --COCO-- bridge;
R is a perhaloalkyl substitutent;
R3 is selected from the group consisting of -hydrogen, -halogen and -phenylthio;
R4 is selected from the group consisting of -hydrogen, -halogen, -lower alkyl, -lower alkoxy, -lower alkoxyalkyl, -lower haloalkoxy, -lower alkylthio, -lower alkylsulfonyl, and -diallylamino; or
R3 and R4 at adjacent ring positions constitute a --OCH2 O--, --CH2 C(CH3)2 O--, or --CF2 CF2 O-- bridge; and
R5 is --hydrogen or -lower alkyl.

Description

This application is a division of application Ser. No. 07/136,045, filed Dec. 21, 1987, now U.S. Pat. No. 4,870,089, which in turn is a continuation-in-part of Ser. No. 06/801,365, filed Nov. 25, 1985, now abandoned.
This invention pertains to the field of benzoylurea insecticides; more specifically, it pertains to novel N-[(alpha-perhaloalkylbenzyloxy)pyridyl]-N'-benzoylurea insecticides, processes and intermediates thereto, insecticidal compositions containing such benzoylurea compounds, and to the use of such compounds for controlling insects.
Certain N-[substituted pyridinyl]-N'-benzoylurea compounds are known as insecticides. For example, U.S. Pat. No. 4,173,639 and U.S. Pat. No. 4,264,605 describe such N'-benzoylurea compounds carrying a N-pyridyl substituent in which the pyridine ring also contains a hydrocarbyloxy group. It is reported that compounds of this type affect insects by interfering with their metamorphosis; that is, they disrupt the normal growth and development pattern.
According to the present invention, adding an alpha-perhaloalkyl substituent to the benzyl group provides insecticides with enhanced activity, controlling certain insects at application rates as low as 1 ppm. Accordingly, the N-[(alpha-perhaloalkylbenzyloxy)pyridyl]-N'-benzoylurea compounds of this invention are described by the formula ##STR2## in which
RA is selected from the group consisting of -hydrogen, -halogen, -lower alkyl, -lower alkoxy, -benzyl, and -benzyloxy;
RB is selected from -hydrogen and -halogen;
RC and RD are both -hydrogen or together constitute a -COCO- bridge;
R is a perhaloalkyl substituent;
R3 is selected from the group consisting of -hydrogen, -halogen and -phenylthio;
R4 is selected from the group consisting of -hydrogen, -halogen, -lower alkyl, -lower alkoxy, -lower alkoxyalkyl, -lower haloalkoxy, -lower alkylthio, -lower, alkylsulfonyl, and -dialllylamino; or
R3 and R4 at adjacent ring positions constitute a --OCH2 O--, --CH2 C(CH3)2 O--, or --CF2 CF2 O-- bridge; and
R5 is -hydrogen or -lower alkyl.
The terms "halo" and "halogen" when employed herein mean fluorine, chlorine or bromine. The term "lower" modifying "alkyl, " "alkoxy," and the like implies a straight or branched hydrocarbon chain of 1-6, preferably 1-3, carbon atoms; "halo" coupled with another term means one or more hydrogen atoms has been replaced by halogen; "perhalo" coupled with another term means all the hydrogen atoms have been replaced by halogen.
Among the aforesaid compounds, the most attractive insecticides results when RA and RB are in the 2-and 6-positions, respectively. In addition, N-(3-pyridinyl) compounds are preferred, with R5 at the 5-position. Additionally, the preferred compounds have the R3 and R4 substituents in the 3- and 4-positions, respectively. Specific compounds of interest include N-[[[[2-(2,2,2-trifluoro-1-phenylethoxy)-3-methyl]pyridin-5-yl]amino]carbonyl]-2-chlorobenzamide, N-[[[[2-(2,2,2-trifluoro-1-phenylethoxy)-3-methyl]pyridin-5-yl]amino]carbonyl]-2-fluorobenzmide, N-[[[[2-[1-(2,3-dihydro-2,2,3,3-tetrafluorobenzofuran-5-yl)]-2,2,2-trifluoroethoxy]-pyridin-5-yl]amino]carbonyl]-2,6-difluorobenzamide, N-[[[[2-(2,2,2-trifluoro-1-phenylethoxy)-3-methyl]pyridin-5-yl]amino]carbonyl]-2,6-difluorobenzamide, N-[[[[2-[1-(1,3-benzodiox-5-yl)-2,2,3,3,4,4,4-heptafluorobutoxy]-3-methyl]pyridin-5-yl]amino]carbonyl]2,6-difluorobenzamide, N-[[[[2-[1-(2,3-dihydro-2,2-dimethylbenzofuran-5-yl)-2,2,3,3,3-pentafluoropropoxy]-3-methyl]pyridin-5-yl]amino]carbonyl]-2,6-difluorobenzamide, 1-[(2,6-difluorophenyl)carbonyl]-3-[2-[1-(1,3-benzodiox-5-yl)-2,2,2-trifluoroethoxy]pyridin-5-yl]imidazolidinetrione, 1-[(2,6-difluorophenyl)carbonyl]-3-[[2-(1-phenyl-2,2,2-trifluoroethoxy)-3-methyl]pyridin-5-yl]imidazolidinetrione, N-[[[[2[2,2,2-trifluoro-1-(4-trifluoromethoxyphenyl)ethoxy]3-methyl]pyridin-5-yl]amino]carbonyl]-2,6-difluorobenzamide, and N-[[[[2-[2,2,2-trifluoro-1-(4-trifluoromethoxyphenyl)ethoxy]-3-methyl]pyridin-5-yl]amino]carbonyl]- 2-chlorobenzamide.
Also within the contemplation of the instant invention are insecticidal compositions comprising an insecticidally effective amount of at least one of the aforesaid benzoylurea compounds in admixture with an agriculturally acceptable carrier. In addition, this invention includes a method of controlling insects which comprises applying to plants upon which the insects feed and where control is desired an insecticidally effective amount of at least one of the aforesaid N-[(alpha-perhaloalkylbenzyloxy)pyridyl]-N'-benzoylurea compounds.
The compounds of this invention can be prepared using general techniques disclosed in U.S. Pat. No. 4,013,717, viz:
Preparation of the compounds of this invention will be clarified by reference to the following Examples.
EXAMPLE 27 N-[[[[2-[1-(2,3-Dihydro-2,2-dimethylbenzofuran-5-yl)-2,2,3,3,3-pentafluoropropoxy]-3-methyl]pyridin-5-yl]amino]carbonyl]-2-chorobenzamide
5-Amino-3-methyl-2-[1-(2,3-dihydro-2,2-dimethylbenzofuran-5-yl)-2,2,3,3,3-pentafluoropropoxy]pyridine was prepared from 2,2,3,3,3-pentafluoro-1-(2,3-dihydro-2,2-dimethylbenzofuran-5-yl)propan-1-one, by the method of Example 42. 2-Chloro-3-methyl-5nitropyridine was used in place of 2-chloro-5-nitropyridine.
In a manner similar to Example 42 the reaction of 2-chlorobenzamide (0.6 g, 0.0037 mole), first with oxalyl chloride (0.5 g, 0.0037 mole) in methylene chloride (10 ml) and toluene (70 ml), followed by reaction with 5-amino-3-methyl-2-[1-(2,3-dihydro-2,2,-dimethylbenzofuran-5-yl)-2,2,3,3,3-pentafluoropropoxy]pyridine (1.5 g, 0.0037 mole), yielded 1.6 g of N-[[[[2-[1-(2,3-dihydro-2,2-dimethylbenzofuran-5-yl)2,2,3,3,3-pentafluoropropoxy]-3-methyl]pyridin-5-yl]amino]carbonyl]-2-chlorobenzamide as a solid (mp 141°-143° C.). The nmr and ir spectra were consistent with the proposed structure.
Analysis: Calc'd for C27 H23 ClF5 N3 O4 : C 55.54; H 3.97; Found: C56.10; H 4.17.
EXAMPLE 42 N-[[[2-[1-(3,4-Dichlorophenyl)-2,2,2-trifluoroethyoxy]pyridin-5-yl]amino]carbonyl]-2,6-difluorobenzamide
Under a dry nitrogen atmosphere a mixture of 3,4-dichloro-alpha,alpha,alpha-trifluoroacetophenone (6.4 g, 0.026 mole) and sodium borohydride (2.0 g, 0.052 mole) in ethanol (100 ml) was stirred at room temperature for approximately 18 hours. The solvent was evaporated under reduced pressure leaving a residue which was dissolved in water. The resultant solution was extracted with two 100 ml portions of methylene chloride. The combined extracts were dried over anhydrous magnesium sulfate and filtered. The filtrate was evaporated under reduced pressure, yielding 6.4 g of 1-(3,4-dichlorophenyl)-2,2,2-trifluoroethanol.
Under a dry argon atmosphere a solution of 2-chloro-5-nitropyridine (1.6 g, 0.010 mole) and 1-(3,4-dichlorophenyl)-2,2,2-trifluoroethanol (2.5 g, 0.010 mole) in dimethyl sulfoxide (50 ml) was stirred for five minutes. Potassium carbonate (1.6 g, 0.011 mole) was added to the mixture in one portion. The resultant mixture was stirred at room temperature for approximately 18 hours. The mixture was transferred to a separatory funnel to which was added 50 g of ice and 75 ml of a 2N aqueous sodium hydroxide solution. This aqueous mixture was extracted with two 200 ml portions of diethyl ether. The combined extracts were dried over anhydrous magnesium sulfate and filtered. The solvent was evaporated from the filtrate under reduced pressure, leaving an oil. Purification of this oil by column chromatography on silica gel yielded 3.3 g of 2-[1-(3,4-dichlorophenyl)-2,2,2-trifluoroethoxy]-5-nitropyridine.
Hydrogenation of 2-[1-(3,4-dichlorophenyl)-2,2,2-trifluoroethoxy]-5-nitropyridine (2.7 g, 0.0074 mole) with plantinum oxide (0.3 g, 0.0013 mole) in methanol (50 ml) yielded 2.5 g of 5-amino-2-[1-(3,4-dichlorophenyl)-2,2,2-trifluoroethoxy]pyridine.
A stirred mixture of 2,6-difluorobenzamide (0.56 g, 0.0036 mole), oxalyl chloride (0.45 g, 0.0036 mole), and methylene chloride (10 ml) in toluene (70 ml) was heated at reflux for three hours. Approximately 10 ml of solvent was removed by distillation under reduced pressure. A solution of 5-amino-2-[1-(3,4-dichlorophenyl)-2,2,2-trifluoroethoxy]pyridine (1.2 g, 0.0036 mole) in toluene (35 ml) was added to the reaction mixture. The resultant solution was stirred at room temperarture for approximately 18 hours. Most of the solvent was evaporated under reduced pressure, leaving a liquid residue. About 150 ml of n-heptane was added to the residue, and the mixture was stirred at room temperature, slowly forming a precipitate. The mixture was cooled in dry ice before collecting the precipitate by filtration. A total of 1.65 g of N-[[[2-[-1-(3,4-dichlorophenyl)2,2,2-trifluoroethoxy]pyridin-5-yl]amino]carbonyl]2,6-difluorobenzamide was collected (mp 171°-172° C.). The nmr and ir spectra were consistent with the proposed structure.
Analysis: Calc'd for C21 H12 Cl2 F5 N3 O3 : C 48.48; H 2.33; Found: C 48.62; H 2.60.
EXAMPLE 66 N-[[[2-[1-(2,2,3,3-Tetrafluorobenzofuran-5-yl)-2,2,2-trifluoroethoxy]-3-methyl]pyridin-5-yl]amino]carbonyl]-2,6-difluorobenzamide
5-Amino-3-methyl-2-(2,2,3,3-tetrafluorobenzofuran-5-yl)-2,2,2-trifluoroethoxy]pyridine was prepared from 1-(2,2,3,3-tetrafluorobenzofuran-5-yl)2,2,2-trifluoroethanone by the method of Example 42. The latter starting material was obtained as follows:
Into a pressure bottle was placed 2-chloro-4nitrophenol (15.0 g, 0.086 mole), potassium carbonate (11.9 g, 0.86 mole), propanethiol (1.5 g, 0.02 mole), 1,2-dibromotetrafluoroethane (33.7 g, 0.13 mole), and N,N-dimethylformamide (115 ml). The pressure bottle was sealed, and the mixture was stirred at 50° C. for 48 hours. The pressure bottle was cooled to room temperature, opened, and the contents poured into a separatory funnel. Approximately 200 ml of a 2N aqueous sodium hydroxide solution was added to the separatory funnel. The resultant mixture was extracted with four 300 ml portions of diethyl ether. The extracts were combined and washed with two 100 ml portions of a 2N aqueous sodium hydroxide solution. The washed extract was dried over anhydrous magnesium sulfate and filtered. The filtrate was evaporated under reduced pressure, leaving an oil. The reaction described above was repeated three additional times. The residual oils form the four experiments were combined and purified by column chromatography on silica gel, eluting with n-heptane:toluene (95:5), yielding 57.6 g of 3-chloro-4-bromo-1,1,2,2-tetrafluoroethoxy)nitrobenzene as an oil.
Into a pressure bottle were placed 3-chloro-4-(2-bromo-1,1,2,2-tetrafluoroethoxy)nitrobenzene (10.0 g, 0.028 mole), copper powder (9.0 g, 0.14 mole, 200 mesh), 2,2'-bipyridyl (0.45 g, 0.0028 mole), and dimethylsulfoxide (40 ml). The pressure bottle was sealed and the reaction mixture was stirred at 190°195° C. for two hours. The pressure bottle was cooled to room temperature, opened, and the contents poured, into a separatory funnel. Approximately 200 ml o a 2N hydrochloric acid solution was added to the separatory funnel. The mixture was extracted with three 150 ml portions of diethyl ether. The extracts were combined and washed in succession with 200 ml of a 2N hydrochloric acid solution, 200 ml of a saturated aqueous sodium chloride solution, and 200 ml of a 2N aqueous sodium hydroxide solution. The washed extract was dried over anhydrous magnesium sulfate and filtered. The solvent was evaporated under reduced pressure, leaving an oil. The reaction described above was repeated six additional times. The residual oils from the seven experiments were combined and subjected to column chromatography on silica gel, eluting with toluene, yielding a yellow oil. This oil was dissolved in 125 ml methylcyclohexane, and the solution was placed in a freezer for approximately 18 hours. Crystals formed and were collected by filtration, yielding 20.7 g of 2,2,3,3-tetrafluoro-5-nitorbenzofuran. The filtrate was evaporated under reduced pressure, leaving an oil. Distillation of this oil under reduced pressure provided an additional 3.0 g of product (bp 75° C./0.2 mm Hg).
Hydrogenation of 2,2,3,3-tetrafluoro-5-nitrobenzene (10.0 g, 0.042 mole) with a catalytic amount of platinum oxide (0.5 g) in methanol (200 ml) produced 8.6 g of 5-amino-2,2,3,3-tetrafluorobenzofuran.
A stirred mixture of 5-amino-2,2,3,3-tetrafluorobenzofuran (5.0 g, 0.024 mole) and hydrobromic acid (7.3 ml of a 48% aqueous solution) and water (10 ml) was cooled to 3° C. in an ice bath. While maintaining a temperature of less than 5° C., a solution of sodium nitrite (1.7 g, 0.024 mole) in water was added. After complete addition this mixture was stirred for a brief period, then was added slowly to a stirred, refluxing mixture of cuprous bromide (6.9 g, 0.024 mole) in hydrobromic acid (10 ml of a 48% aqueous solution). After complete addition the mixture was stirred at reflux for 20 minutes, then allowed to cool to room temperature. The reaction mixture was poured into a separatory funnel and diluted with ice water. This mixture was extracted several times with diethyl ether. The extracts were combined and washed first with 100 ml of an aqueous saturated sodium chloride solution, then with two 100 ml portions of a 2N aqueous sodium hydroxide solution. The washed organic phase was dried over anhydrous magnesium sulfate and filtered. The filtrate was evaporated at atmospheric pressure, yielding 5.9 g of 5-bromo-2,2,3,3-tetrafluorobenzofuran as an oil.
The reaction of 5-bromo-2,2,3,3-tetrafluorobenzofuran (5.3 g, 0.02 mole) with magnesium turnings (0.48 g) in dry diethyl ether was followed by reaction with N-methoxy-N-methyltrifluoroacetamide (3.5 g, 0.022 mole), yielding 5.3 g of 1-(2,2,3,3-tetrafluorobenzofuran-5-yl)-2,2,2-trifluoroethanone.
In a manner similar to Example 42 the reaction of 2,6-difluorobenzamide (0.3 g, 0.0019 mole), first with oxalyl chloride (0.3 g, 0.0021 mole) in methylene chloride (5 ml) and toluene (50 ml), followed by reaction with 5-amino-3-methyl-2-[1-(2,2,3,3-tetrafluorobenzofuran-5-yl)-2,2,2-trifluoroethoxy]pyridine (0.8 g, 0.0019 mole) yielded 0.8 g of N-[[[[2-[1-(2,2,3,3-tetrafluorobenzofuran-5-yl)-2,2,2-trifluoroethoxy]-3-methyl]pyridine-5-yl]amino]carbonyl]2,6-difluorobenzamide as an oil. The nmr and ir spectra were consistent with the proposed structure.
Analysis: Calc'd for C24 H14 F9 N3 O4 : C 49.75; H 2.43; Found: C 47.47; H 2.26.
EXAMPLE 84 1-[(2,6-Difluorophenyl)carbonyl]-3-[2-[1-(3,4-dichlorophenyl)-2,2,2-trifluoroethoxy]pyridine-5-yl]imidazolidinetrione
To a stirred solution of N-[[[2-[1-(3,4-dichlorophenyl)-2,2,2-trifluoroethoxy]pyridin-5-yl]amino]carbonyl]2,6-difluorobenzamide (1.0 g, 0.002 mole) in 1,2-dichloroethane (10 ml) was added oxalyl chloride (0.24 g, 0.0020 mole). This mixture was heated at reflux for five days. Additional oxalyl chloride (0.24 g) was added, and refluxing was continued for one more day. The solvent was removed from the reaction mixture by distillation under reduced pressure, leaving an oil. This oil was purified by column chromatography on silica gel, elution with toluene: ethyl acetate (9:1), yielding 0.84 g of 1-[(2,6-difluorophenyl)carbonyl]-3-[2-[1-(3,4-dichlorphenyl)2,2,2-trifluoroethoxy]pyridin-5-yl]imidazolidinetrione as a solid (mp 160° C.). The nmr and ir spectra were consistent with the proposed structure.
Analysis: Calc'd for C23 H10 Cl2 F3 N3 O5 : C 48.11; H 1.76; Found: C 47.15; H 1.69.
Additional Examples prepared by similar techniques appear in Table 1.
In the normal use of the insecticidal benzoylureas of the present invention, the benzoylureas usually will not be employed free from admixture or dilution, but ordinarily will be used in a suitable formulated composition compatible with the method of application and comprising an insecticidally effective amount of benzoylurea. The benzoylureas of this invention, like most pesticidal agents, may be blended with the agriculturally acceptable surface-active agents and carriers normally employed for facilitating the dispersion of active ingredients, recognizing the accepted fact that the formulation and mode of application of an insecticide may affect the activity of the material. The present benzoylureas may be applied, for example, as sprays, dusts, or granules to the area where pest control is desired, the type of application varying of course with the pest and the environment. Thus, the benzoylureas of this invention may be formulated as granules of large particle size, as powdery dusts, as wettable powders, as emulsifiable concentrates, as solutions, and the like.
Granules may comprise porous or nonporous particles, such as attapulgite clay or sand, for example, which serve as carriers for the benzoylureas. The granule particles are relatively large, a diameter of about 400-2500 microns typically. The particles are either impregnated with the benzoylurea from solution or coated with the benzoylurea, adhesive sometimes being employed. Granules generally contain 0.05-10%, preferably 0.5-5%, active ingredient as the insecticidally effective amount.
Dusts are admixtures of the benzoylureas with finely divided solids such as talc, attapulgite clay, kieselguhr, pyrophyllite, chalk, diatomaceous earths, calcium phosphates, calcium and magnesium carbonates, sulfur, flours, and other organic and inorganic solids which act as carriers for the insecticide. These finely divided solids have an average particle size of less than about 50 microns. A typical dust formulation useful for controlling insects contains 1 part of benzoylurea, such as N-[[[[2-(2,2,2-trifluoro-1-phenylethoxy)-3-methyl]pyridin-5-yl]amino]carbonyl]-2-chlorobenzamide, and 99 parts of talc.
The benzoylureas of the present invention may be made into liquid concentrates by dissolution or emulsification in suitable liquids and into solid concentrates by admixture with talc, clays, and other known solid carriers used in the pesticide art. The concentrates are compositions containing, as an insecticidally effective amount, about 5-50% benzoylurea, such as N-[[[[2-(2,2,2-trifluoro-1-phenylethoxy)-3-methyl]pyridin-5-yl]amino]carbonyl]-2-chlorobenzamide, and 95-50% inert material, which includes surfaceactive dispersing, emulsifying, and wetting agents, but even higher concentrations of active ingredient may be employed experimentally. The concentrates are diluted with water or other liquids for practical application as sprays, or with additional solid carrier for use as dusts.
Typical carriers for solid concentrates (also called wettable powders) include fuller's earth, clays, silicas, and other highly absorbent, readily wetted inorganic diluents. A solid concentrate formulation useful for controlling insects contains 1.5 parts each of sodium lignosulfonate and sodium laurylsulfate as wetting agents, 25 parts of N-[[[[2-(2,2,2-trifluoro-1-phenylethoxy)-3-methyl]pyridin-5-yl]amino]carbonyl]-2-chlorobenzamide, and 72 parts of attapulgite clay.
Manufacturing concentrates are useful for shipping low melting products of this invention. Such concentrates are prepared by melting the low melting solid products together with one percent or more of a solvent to produce a concentrate which does not solidify on cooling to the freezing point of the pure product or below.
Useful liquid concentrates include the emulsifiable concentrates, which are homogeneous liquid or paste compositions readily dispersed in water or other liquid carriers. They may consist entirely of the benzoylurea with a liquid or solid emulsifying agent, or they may also contain a liquid carrier such as xylene, heavy aromatic naphthas, isophorone and other relatively nonvolatile organic solvents. For application, these concentrates are dispersed in water or other liquid carriers and normally applied as sprays to areas to be treated.
Typical surface-active wetting, dispersing, and emulsifying agents used in pesticidal formulations include, for example, the alkyl and alkylaryl sulfonates and sulfates and their sodium slats; alkylamide sulfonates, including fatty methyl taurides; alkylaryl polyether alcohols, sulfated higher alcohols, polyvinyl alcohols; polyethylene oxides; sulfonated animal and vegetable oils; sulfonated petroleum oils; fatty acid esters of polyhydric alcohols and the ethylene oxide addition products of such esters; and the addition products of long-chain mercaptans and ethylene oxide. Many other types of useful surface-active agents are available in commerce. The surface-active agent, when used, normally comprises about 1-15% by weight of the insecticidal composition.
Other useful formulations include simple solutions of the active ingredient in a solvent in which it is completely soluble at the desired concentration, such as acetone or other organic solvents.
An insecticidally effective amount of benzoylurea in an insecticidal composition diluted for application is normally in the range of about 0.001% to about 8% by weight. Many variations of spraying and dusting compositions known in the art may be used by substituting the benzoylureas of this invention into compositions known or apparent in the art.
The insecticidal compositions of this invention may be formulated with other active ingredients, including other insecticides, nematicides, acaricides, fungicides, plant growth regulators, fertilizers, etc. In using the compositions to control insects, it is only necessary that an insecticidally effective amount of benzoylurea be applied to plants upon which insects feed and whose control is desired. For most applications, an insecticidally effective amount will be about 0.1-2.0 kg/ha.
The benzoylureas of this invention were tested by incorporating the compounds into the diet of second instar southern armyworm (Spodoptera eridania) and cabbage looper (Trichoplusia ni). The tests were conducted at rates of 200, 20, and 2 ppm, using ten larvae per replicate and two replicates per rate. Each test was read one day, three to five days, and six to eleven days after infestation to determine the number dead after at least one molt.
The test media consisted of a clay formulation (dust) of the test compound mixed with the insect diet. The components of the test media were:
______________________________________
              Parts by Weight
______________________________________
Pinto beans     12.90
Wheat germ      5.68
Brewer's dried yeast
                3.64
Ascorbic acid   0.37
Methyl paraben  0.23
Sorbic acid     0.11
Sodium benzoate   0.00284
Agar            0.71
Formalin (40%)  0.23
Water           76.13
                100.00
______________________________________
The agar was dissolved with heating in one-half the water and was brought to a boil. Simultaneously, all other ingredients except the formalin were placed in a blender with the remaining water and were reduced to a smooth, homogenous mixture. This mixture was added to the boiling agar. Immediately, the formalin was added with mixing.
The compounds of this invention were formulated as a dust on a clay base. The dust consisted of the following:
______________________________________
Clay Formulation    5% Dust
______________________________________
Test compound        5.00
Base                95.00
96%      Attaclay
2%       highly purified sodium
         lignosulfonate (100%)
2%       powdered sodium alkyl-
         naphthalene sulfonate (75%)
                        100.00
______________________________________
These formulations were prepared by mixing the active ingredient (i.e. the test compound) with the dry base.
Test media containing 200 ppm of the test compound were prepared by making a `stock solution` from 1000 mg of a 5% dust formulation stirred well with 5 ml of distilled water in a vial. One milliliter of the `stock solution` was added to 50 ml of warm, i.e. molten, insect diet in a plastic petri dish which was then mixed thoroughly. After cooling to room temperature, the gelled test media were infested with test larvae and covered.
Lower test rates were prepared by dilution of the `stock solution` according to the following table:
______________________________________
Desired Rate ml of           ml of
(ppm)        `stock solution`
                             water
______________________________________
20           1               9
 2           1 ml of 20 ppm solution
                             9
______________________________________
The results of diet incorporated testing are summarized in Table 2.
                                  TABLE 1
__________________________________________________________________________
Insecticidal N-[(Alpha-perhaloalkylbenzyloxy)pyridyl]-
N'-benzoylureas
 ##STR4##
Example
     R.sub.A
        R.sub.B
              R.sub.5
                 R   R.sub.3
                         R.sub.4   mp (°C.)
__________________________________________________________________________
 1   H  H     CH.sub.3
                 CF.sub.3
                     H   H         155-158
 2   H  Cl    H  CF.sub.3
                     H   H         162-163
 3   H  Cl    H  C.sub.2 F.sub.5
                     H   H         149-149.5
 4   H  Cl    H  C.sub.3 F.sub.7
                     H   H         129
 6   H  Cl    H  CF.sub.3
                     SC.sub.6 H.sub.5
                         H         161-163
 7   H  Cl    H  C.sub.3 F.sub.7
                     H   SCH.sub.3 124-127
 8   H  Cl    H  CF.sub.3
                     Cl  Cl        111-112
 9   H  Cl    H  C.sub.2 F.sub.5
                     Cl  Cl        129-131
10   H  Cl    H  C.sub.3 F.sub.7
                     Cl  Cl        119-123
11   H  Cl    H  CF.sub.3
                     OCH.sub.2 O   116-119
12   H  Cl    H  C.sub.2 F.sub.5
                     OCH.sub.2 O   121
13   H  Cl    H  C.sub.3 F.sub.7
                     OCH.sub.2 O   145
14   H  Cl    H  C.sub.2 F.sub.5
                     CH.sub.2 C(CH.sub.3).sub.2 O
                                   149-154
15   H  Cl    H  C.sub.3 F.sub.7
                     CH.sub.2 C(CH.sub.3).sub.2 O
                                   163-163.5
16   H  Cl    CH.sub.3
                 CF.sub.3
                     H   H         142-145
17   H  Cl    CH.sub.3
                 C.sub.2 F.sub.5
                     H   H         124-125
18   H  Cl    CH.sub.3
                 C.sub.3 F.sub.7
                     H   H
20   H  Cl    CH.sub.3
                 CF.sub.3
                     H   Cl        115
21   H  Cl    CH.sub.3
                 CF.sub.3
                     Cl  Cl
22   H  Cl    CH.sub.3
                 C.sub.2 F.sub.5
                     Cl  Cl        90-94
23   H  Cl    CH.sub.3
                 C.sub.3 F.sub.7
                     Cl  Cl        131-133
24   H  Cl    CH.sub.3
                 CF.sub.3
                     OCH.sub.2 O
25   H  Cl    CH.sub.3
                 C.sub.2 F.sub.5
                     OCH.sub.2 O   144
26   H  Cl    CH.sub.3
                 C.sub.3 F.sub.7
                     OCH.sub.2 O   63
27   H  Cl    CH.sub.3
                 C.sub.2 F.sub.5
                     CH.sub.2 C(CH.sub.3).sub.2 O
                                   141-143
28   H  Cl    CH.sub.3
                 C.sub.3 F.sub.7
                     CH.sub.2 C(CH.sub.3).sub.2 O
                                   152-155
29   H  Cl    CH.sub.3
                 C.sub.3 F.sub.7
                     Cl  N(CH.sub.2 CHCH.sub.2).sub.2
                                   oil
30   H  F     CH.sub.3
                 CF.sub.3
                     H   H
31   H  CH.sub.3
              CH.sub.3
                 CF.sub.3
                     H   H         122-123
32   H  C.sub.2 H.sub.5
              CH.sub.3
                 CF.sub.3
                     H   H         103-104
33   H  CH.sub.2 C.sub.6 H.sub.5
              CH.sub.3
                 CF.sub.3
                     H   H         89-91
34   H  OCH.sub.3
              CH.sub.3
                 CF.sub.3
                     H   H         139-142
35   H  OCH.sub.2 C.sub.6 H.sub.5
              CH.sub.3
                 CF.sub.3
                     H   H         104-106
36   F  F     H  CF.sub.3
                     H   H         172-174
37   F  F     H  C.sub.2 F.sub.5
                     H   H         193-195
38   F  F     H  C.sub.3 F.sub.7
                     H   H         137
40   F  F     H  CF.sub.3
                     SC.sub.6 H.sub.5
                         H         102-103.5
41   F  F     H  C.sub.3 F.sub.7
                     H   SCH.sub.3 132-135
42   F  F     H  CF.sub.3
                     Cl  Cl        171-172
43   F  F     H  C.sub.2 F.sub.5
                     Cl  Cl        164-167
44   F  F     H  C.sub.3 F.sub.7
                     Cl  Cl        158-160
45   F  F     H  CF.sub.3
                     OCH.sub.2 O   165-167
46   F  F     H  C.sub.2 F.sub.5
                     OCH.sub.2 O   183
47   F  F     H  C.sub.3 F.sub.7
                     OCH.sub.2 O   103
48   F  F     H  CF.sub.3
                     CH.sub.2 C(CH.sub.3).sub.2 O
                                   122
49   F  F     H  C.sub.2 F.sub.5
                     CH.sub.2 C(CH.sub.3).sub.2 O
                                   163-167
50   F  F     H  C.sub.3 F.sub.7
                     CH.sub.2 C(CH.sub. 3).sub.2 O
                                   164-167
51   F  F     H  CF.sub.3
                     CF.sub.2 CF.sub.2 O
                                   162-163.5
52   F  F     CH.sub.3
                 CF.sub.3
                     H   H         143-145
53   F  F     CH.sub.3
                 C.sub.2 F.sub.5
                     H   H         121-122
54   F  F     CH.sub.3
                 C.sub.3 F.sub.7
                     H   H         102
56   F  F     CH.sub.3
                 CF.sub.3
                     H   Cl        145
57   F  F     CH.sub.3
                 CF.sub.3
                     Cl  Cl
58   F  F     CH.sub.3
                 C.sub.2 F.sub.5
                     Cl  Cl        119-122
59   F  F     CH.sub.3
                 C.sub.3 F.sub.7
                     Cl  Cl        132-132.5
60   F  F     CH.sub.3
                 CF.sub.3
                     OCH.sub.2 O   167
61   F  F     CH.sub.3
                 C.sub.2 F.sub.5
                     OCH.sub.2 O   144
62   F  F     CH.sub.3
                 C.sub.3 F.sub.7
                     OCH.sub.2 O   94
63   F  F     CH.sub.3
                 CF.sub.3
                     CH.sub.2 C(CH.sub.3).sub.2 O
                                   115
64   F  F     CH.sub.3
                 C.sub.2 F.sub.5
                     CH.sub.2 C(CH.sub.3).sub.2 O
                                   135-140
65   F  F     CH.sub.3
                 C.sub.3 F.sub.7
                     CH.sub.2 C(CH.sub.3).sub.2 O
                                   140-143
66   F  F     CH.sub.3
                 CF.sub.3
                     CF.sub.2 CF.sub.2 O
                                   oil
67   Cl F     CH.sub.3
                 CF.sub.3
                     H   H         171-175
68   Cl CH.sub.3
              CH.sub.3
                 CF.sub.3
                     H   H         164-167
69   F  F     H  CClF.sub.2
                     H   H         191-192
70   F  F     CH.sub.3
                 CClF.sub.2
                     H   H         107-110
71   F  F     CH.sub.3
                 C.sub.3 F.sub.7
                     Cl  N(CH.sub.2 CHCH.sub.2).sub.2
                                   oil
72   F  F     CH.sub.3
                 CClF.sub.2
                     F   CH.sub.3  163-165
73   H  3-F   CH.sub.3
                 CF.sub.3
                     H   H         180-181
74   H  7-F   CH.sub.3
                 CF.sub.3
                     H   H
 77* H  Cl    H  CF.sub.3
                     H   SC.sub.6 H.sub.5
 78* H  Cl    H  C.sub.3 F.sub.7
                     H   SCH.sub.3
 79* H  Cl    H  CF.sub.3
                     Cl  Cl        149-152
 80* H  Cl    H  CF.sub.3
                     OCH.sub.2 O   134
 81* H  Cl    CH.sub.3
                 CF.sub.3
                     H   H
 82* H  Cl    CH.sub.3
                 C.sub.2 F.sub.5
                     H   H
 83* F  F     H  C.sub.3 F.sub.7
                     H   SCH.sub.3
 84* F  F     H  CF.sub.3
                     Cl  Cl        160
 85* F  F     H  CF.sub.3
                     OCH.sub.2 O   164
 86* F  F     H  C.sub.2 F.sub.5
                     CH.sub.2 C(CH.sub.3).sub.2 O
                                   184
 87* F  F     CH.sub.3
                 CF.sub.3
                     H   H         67
 88* F  F     CH.sub.3
                 C.sub.2 F.sub.5
                     H   H
89   Cl H     CH.sub.3
                 CF.sub.3
                     H   OC.sub.2 H.sub.5
                                   167
90   F  F     CH.sub.3
                 CF.sub.3
                     H   OC.sub.2 H.sub.5
                                   137
91   Cl H     CH.sub.3
                 CF.sub.3
                     H   CH.sub.2 OCH.sub.3
                                   163-167
92   Cl H     CH.sub.3
                 CF.sub.3
                     H   SCH.sub.3 151
93   F  F     CH.sub.3
                 CF.sub.3
                     H   SCH.sub.3 151
94   Cl H     CH.sub.3
                 CF.sub.3
                     H   SO.sub.2 CH.sub.3
                                   134
95   F  F     CH.sub.3
                 CF.sub.3
                     H   SO.sub.2 CH.sub.3
                                   180
96   F  F     CH.sub.3
                 CF.sub.3
                     H   OCF.sub.3 161
97   Cl H     CH.sub.3
                 CF.sub.3
                     H   OCF.sub.3 139
98   F  F     CH.sub.3
                 CF.sub.3
                     H   CH.sub.2 OCH.sub.3
                                   140-144
__________________________________________________________________________
 *R.sub.C and R.sub.D together constitute a COCObridge.

              TABLE 2
______________________________________
Diet Incorporated Tests
% Kill
(5% Formulation on Clay)
Exposure    Insects Tested.sup.a and Rate
Cpd. of
      Period    SAW (ppm)     CL (ppm)
Ex.   (Days)    200    20    2    200  20   2
______________________________________
 1    5         100    100    0   100  100  10
 2    4         70     80    60   100  100  90
 3    5         100    100   100  100  100  80
 4    4         90     90    90   100  100  80
 6    4         100     0    10    20   0    0
 7    4         100    70     0    60   10   0
 8    4          0     50    70   100  100   0
 9    3         60     100   30   100   70   0
10    4         90     100   70   100   0    0
11    8         20      0     0   100  100   0
12    6         60     10     0   100   60  20
13    5         90     30     0    90    40  0
14    6         10     100    0    90   10   0
15    7         100    100   90   100   40   0
16    5         90     100   100  100  100  100
17    5         100    100   100  100  100  100
18    4         70     100    0   100  100   0
20    4         100    100   100  100  100  90
21    4         10     60     0    80   0    0
22    7         100    100   60   100   90  10
23    4         100    80    60    80   0    0
24    4         60     50     0    10   80  10
25    3          0     50     0    90   40   0
26    6         80     60     0   100   40  10
27    8         100    60     0   100   70   0
28    4         100    80    30    50   0    0
29    8         10     30    10    10   0    0
30    4         100    80    20    90  100  30
31    5         100    100   100  100  100  20
32    8         50     10     0    0    0    0
33    8          0      0     0    0    0   10
34    5         100     0     0    0    0   10
35    8         30      0     0    10   0    0
36    4         70     80    60   100  100  90
37    5         100    90    100  100  100  100
38    7         90     100   100   90  100  100
40    5         30     50    10    90   80   0
41    5         100    100    0   100  100  10
42    4         60     60    90    80  100  80
43    3         80     90    60   100   80  30
44    4         100    100   100  100  100   0
45    5         10     10    20    90   80  10
46    6         100    100    0   100  100   0
47    5         30     50    10    90   80   0
48    4         100    100   80    90   80  80
49    8         100    100         50   60  10
50    4         90     100   60   100  100   0
51    5         100    100   100  100  100  100
52    5         100    100   100  100  100  100
53    5         90     100   100  100  100  100
54    4         70     90    100  100  100  100
56    4         100    100   100   80   90  70
57    4         40     70    90    20   40   0
58    7         100    100   90   100  100  10
59    4         100    100   90   100  100  10
60    4         30     30     0    90   30   0
61    3         10     50    10   100   80   0
62    6         70     50     0   100   90   0
63    4         100    100   70    80  100  80
64    2         20      0     0    40   40   0
65    4         100    100   50   100   30   0
66    4         60     70    100  100  100  90
67    4         100    100   100   90  100  40
68    5         100    100    0   100  100  10
69    4         100    100   80   100  100  100
70    4         90     100   90   100  100  80
71    8         70     20    30    0    0   10
72    5         100    100   60   100   80  70
73    4          0     10     0    0    0    0
74    4         70      0     0    20   10  10
77    4         80      0     0   100   0    0
78    4         100     0     0   100   0    0
79    9         100    100   40   100  100  20
80    8          0     70    20   100   30   0
81    5         100    100    0   100   90   0
82    5         90     100   10   100  100   0
83    4         100    100    0   100   80   0
84    4         100    90    40   100   80   0
85    8         90     10         100   40  10
86    8         60      0    10    50   0    0
87    3         70     80    100  100   90  80
88    5         100    100   10    90   90  70
89    5                           100   .sup.  85.sup.b
                                            .sup. 75.sup.c
90    5                           100  .sup. 100.sup.b
                                            .sup. 100.sup.c
91    5                           100   .sup. 90.sup.b
                                            .sup. 45.sup.c
92    5                           100   0    0
93    5                           100   15   0
94    5                            95   10   0
95    5                            95   25   0
96    5                           100  100  75
97    5                           100  100  100
98    5                           100   .sup. 95.sup.b
                                            .sup. 50.sup.c
______________________________________
 .sup.a SAW = Southern armyworm
 CL = Cabbage looper
 .sup.b 10 ppm
 .sup.c 5 ppm

Claims (23)

What is claimed is:
1. An insecticidal benzoylurea compound of the formula ##STR5## wherein RA is selected from the group consisting of -hydrogen, -halogen, -lower alkyl, -lower alkoxy, -benzyl, and -benzyloxy;
RB is selected from -hydrogen and -halogen;
RC and RD together constitute a --COCO-- bridge;
Rα is a lower perhaloalkyl substituent;
R3 is selected from the group consisting of -hydrogen, -halogen and -phenylthio, and R4 is selected from the group consisting of -hydrogen, -halogen, -lower alkyl, -lower alkoxy, -lower alkoxyalkyl, -lower haloalkoxy, -lower alkylthio, -lower alkylsulfonyl, and -diallylamino; or R3 and R4 together constitute a --OCH2 O--, --CH2 C(CH3)2 O--, or --CF2 CF2 O-- bridge; and
R5 is --hydrogen or --lower alkyl.
2. An insecticidal compound of claim 1 wherein
R3 is selected from the group consisting of -hydrogen, --halogen and --phenylthio; and
R4 is selected from the group consisting of -hydrogen, -halogen, -lower alkyl, -lower alkoxy, -lower alkoxyalkyl, -lower haloalkoxy, -lower alkylthio, -lower alkylsulfonyl, and -diallylamino.
3. An insecticidal compound of claim 1 wherein R3 and R4 together constitute a --OCH2 O--, --CH2 C(CH3)2 O--, or --CF2 CF2 O-- bridge.
4. 1-[(2,6-difluorophenyl)carbonyl]-3-[2-[1-(1,3-benzodiox-5-yl)-2,2,2-trifluoroethoxy]pyridin-5-yl]imidazolidinetrione, a compound of claim 1.
5. 1-[(2,6-difluorophenyl)carbonyl]-3-[[2-(1-phenyl2,2,2-trifluoroethoxy)-3-methyl]pyridin-5-yl]imidazolidinetrione, a compound of claim 1.
6. An insecticidal composition comprising in admixture with an agriculturally acceptable carrier a compound of the formula ##STR6## wherein RA is selected from the group consisting of -hydrogen -halogen, -lower alkyl, -lower alkoxy, -benzyl, and -benzyloxy;
RB is selected from -hydrogen and -halogen;
RC and RD together constitute a --COCO-- bridge;
Rα is a lower perhaloalkyl substituent;
R3 is selected from the group consisting of -hydrogen, -halogen and -phenylthio, and R4 is selected from the group consisting of -hydrogen, -halogen, -lower alkyl, -lower alkoxy, -lower alkoxyalkyl, -lower haloalkoxy, -lower alkylthio, -lower alkylsulfonyl, and -diallylamino; or R3 and R4 together constitute a --OCH2 O--, --CH2 C(CH3)2 O--, or --CF2 CF2 O-- bridge; and
R5 is -hydrogen or -lower alkyl.
7. An insecticidal composition of claim 6 wherein
R3 is selected from the group consisting of -hydrogen, -halogen and -phenylthio; and
R4 is selected from the group consisting of -hydrogen, -halogen, -lower alkyl, -lower alkoxy, -lower alkoxyalkyl, -lower haloalkoxy, -lower alkylthio, -lower alkylsulfonyl, and -diallylamino.
8. An insecticidal composition of claim 6 wherein R3 and R4 together constitute a --OCH2 O--, --CH2 C(CH3)2 O--, or --CF2 CF2 O-- bridge.
9. An insecticidal composition of claim 6 wherein said compound is 1-[(2,6-difluorophenyl)carbonyl[-3-[2-[1-(1,3-benzodiox-5-yl)-2,2,2-trifluoroethoxy]pyridin-5yl]imidazolidinetrione.
10. A method for controlling insects which comprises applying to plants upon which insects feed and whose control is desired an insecticidally effective amount of a compound of the formula ##STR7## wherein RA is selected from the group consisting of -hydrogen, -halogen, -lower alkyl, -lower alkoxy, -benzyl, and -benzyloxy;
RB is selected from -hydrogen and -halogen;
RC and RD together constitute a -COCO- bridge;
Rα is a lower perhaloalkyl substituent;
R3 is selected from the group consisting of -hydrogen, -halogen and -phenylthio, and R4 is selected from the group consisting of -hydrogen, -halogen, -lower alkyl, -lower alkoxy, -lower alkoxyalkyl, -lower haloalkoxy, -lower alkylthio, -lower alkylsulfonyl, and -diallylamino; or R3 and R4 together constitute a --OCH2 O--, --CH2 C(CH3)2 O--, or --CF2 CF2 O-- bridge; and
R5 is -hydrogen or -lower alkyl.
11. The method of claim 10 wherein
R3 is selected from the group consisting of -hydrogen, -halogen and -phenylthio; and
R4 is selected from the group consisting of -hydrogen, -halogen, -lower alkyl, -lower alkoxy, -lower alkoxyalkyl, -lower haloalkoxy, -lower alkylthio, -lower alkylsulfonyl, and -diallylamino.
12. The method of claim 10 wherein R3 and R4 together constitute a --OCH2 O--, --CH2 C(CH3)2 O--, or --CF2 CF2 O-- bridge.
13. An insecticidal benzoylurea compound of the formula ##STR8## wherein RA is selected from the group consisting of -hydrogen, -halogen, -lower alkyl, -lower alkoxy, -benzyl, and -benzyloxy;
RB is selected from -hydrogen and -halogen;
RC and RD are both -hydrogen;
Rα is a lower perhaloalkyl substituent;
R3 and R4 together constitute a --OCH2 O--, --CH2 C(CH3)2 O--, or --CF2 CF2 O-- bridge; and
R5 is -hydrogen or -lower alkyl.
14. N-[[[[2-[1-(2,3dihydro-2,2,3,-tetrafluorobenzofuran-5-yl)]-2,2,2-trifluoroethoxy]pyridin-5-yl]amino]carbonyl]-2,6-difluorobenzamide, a compound of claim 13.
15. N-[[[[2-[1-(1,3-benzodiox-5-yl)-2,2,3,3,4,4,4-heptafluorobutoxy]-3-methyl]pyridin-5-yl]amino]carbonyl]-2,6-difluorobenzamide, a compound of claim 13.
16. An insecticidal composition comprising in admixture with an agriculturally acceptable carrier a compound of the formula ##STR9## wherein RA is selected from the group consisting of -hydrogen, -halogen, -lower alkyl, -lower alkoxy, -benzyl, and -benzyloxy;
RB is selected from -hydrogen and -halogen;
RC and RD are both -hydrogen;
Rα is a lower perhaloalkyl substituent;
R3 and R4 together constitute a --OCH2 O--, --CH2 C(CH3)2 O--, or --CF2 CF2 O-- bridge; and
R5 is -hydrogen or -lower alkyl.
17. An insecticidal composition of claim 16 wherein said compound is N-[[[[2-[1-(2,3-dihydro-2,2,3,3-tetrafluorobenzolfuran-5-yl)]-2,2,2-trifluoroethoxy 2,6-difluorobenzamide.
18. An insecticidal composition of claim 17 wherein said compound is N-[[[[2-[1-(1,3-benzodiox-5-yl-2,2,3,3,4,4,4-heptafluorobutoxy]-3-methyl]pyridin-5-yl]amino]carbonyl]-2,6-difluorobenazmide.
19. An insecticidal composition of claim 17 wherein said compound is N-[[[[2-[1-(2,3-dihydro-2,2-dimethylbenzofuran-5yl)-2,2,3,3,3-pentafluoropropoxy]-3-methyl]pyridin-5-yl]amino]carbonyl]-2,6-difluorobenzamide.
20. A method for controlling insects which comprises applying to plants upon which insects feed and whose control is desired an insecticidally effective amount of a compound of the formula ##STR10## wherein RA is selected from the group consisting of -hydrogen, -halogen, -lower alkyl, -lower alkoxy, -benzyl, and -benzyloxy;
RB is selected from -hydrogen and -halogen;
RC and RD are both -hydrogen;
Rα is a lower perhaloalkyl substitutent;
R3 and R4 together constitute a --OCH2 O--, --CH2 C(CH3)2 O--, or --CF2 CF2 O-- bridge; and
R5 is -hydrogen or -lower alkyl.
21. The method of claim 20 wherein said compound is N-[[[[2-[1-(2,3-dihydro-2,2,3,3-tetrafluorobenzofuran-5-yl)]-2,2,2-trifluoroethoxy]pyridin-5-yl]amino]arbonyl]-2,6difluorobenzamide.
22. The method of claim 20 wherein said compound is N-[[[[2-[1-(1,3-benzodiox-5yl)-2,2,3,3,4,4,4-heptafluorobutoxy]-3-methyl]pyridin-5yl]amino]carbonyl]-2,6-difluorobenzamide.
23. The method of claim 20 wherein said compound is N-[[[[2-[1-(2,3-dihydro-2,2-dimethylbenzofuran-5-yl)-2,2,3,3,3-pentafluoropropoxy]-3-methyl]pyridin-5-yl]amino]carbonyl]-2,6-difluorobenzamide.
US07/374,902 1987-12-21 1989-06-30 N-[(alpha-perhaloalkylbenzyloxy)pyridyl]N'-benzoylurea insecticides Expired - Fee Related US5008277A (en)

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